Process for improving the dyeing properties of artificial fibers, foils, films, ribbons, and the like, and products obtained therefrom



Patented F eb. 18, 1941 PATENT OFFICE I z,zsz,s1s

raocsss roa ,nuraovma 'rnr: DYEING FOILS, FILMS, RIBBONS, AND THE LIKE, AND PRODUCTS OBTAINED THEBEFDOM Paul Euelmann, Wollen, Kreis Bitterleld, and

Jose! Diislng, neesauioGei-many,

meme al gnments, New York, N. Y.

assignors, by Walther H. Duisberg,

No Drawing. Application'August 4, 1938, Serial No. 223,012. In Germany August 4, 1937 9 Claim.

This invention relates to a process of producing artificial fibers, films, foils, ribbons and the like materials capable of being dyed by acid wool dyestufis.

It has been proposed to spin artificial fibers, such as rayon or rayon staple fibers from a viscose solution to which have been added protein substances. In this process the protein is added to the spinning solution only shortly before the 10 spinning in order to avoid any substantial degradation of the protein molecule.

In order to fix the incorporated proteins it has further been proposed to condense the fibers with formaldehyde or to treat them subsequently with 5 an amine.

It appeared, however, that a complete fixation of the protein substances within the cellulosic fibers has not been achieved in this manner.

It is therefore an object of the present inven- 20 tion to provide a process by which artificial textile materials capable of beingdyed iastlyby acid wool dyestufi's may be obtained.

A further object 01' the invention is the provision of artificial fibers which can be dyed together 25 with wool and in thesame dyeing bath in 'uniform tints.

Still another object is the provision of artificial fibers, threads and the like textile materials, which consist of cellulose hydrate, cellulose 30 acetate or a similar filmor fiber-forming polymer' and which contain dispersed therein an addition of a basic artificial resin.

Further objects 01' the invention will become apparent from the following detailed specifi- 35 cation.-

In our copending application of even date Ser. No. 223,013, we have described a new type of resinous compositions which are obtained by reacting an organic amine on a protein substance, and jointly polymerizing the reaction product together with an arylisocyanate or an arylisothiocyanate.

As suitable starting materials for the poly-.

merization described in more detail in the said 45 copending application the following may be named as examples.

Suitable organic bases are, for instance, the alkyleneimines, such as ethylene-, propyleneand butylene-imines, N-propyl-ethyleneimine and 50 N-benzylethyleneimine.

Flu'thermore aliphatic and aromatic amines, such as methylamine, stearylamine andaniline may be employed. 5

Suitable protein substances are casein, albu- 55 men, gelatin, and the like materials.

As arylisoand arylisothiocyanates there may be employed mainly the phenyland naphthylis'ocyanates as well as the phenyland naphthylisothiocyanates, benzylisocylenate, and related compounds :We have found that by incorporating the reslnous compositions produced according to the process referred to above in the spinning solutions for artificial fibers or in the casting solutions for films, foils, ribbons and the like materials, products may be obtained which can be dyed easily by acid dyestuffs. The products have the further advantage that the dyeings with acid dyestuffs are exceedingly Test against light and washing and that they resemble the dyeings on wool in all respects.

The resinous compositions may be added to the spinning 'solutions'either in the form of the reaction mixture or they may be isolated beforehand and added to the spinning solutions as powdery substances.

It is further possible to produce an emulsion of the resinous compositions by adding solvents thereof and to add this emulsionto the spinning solutions.

Surprisingly it has proved that'the spinning solutions are not affected at all by these additions and that the spinning or casting may be eflected in exactly the same manner as has hitherto been usual. No dimculties arise at all from the addition oLthe synthetic resins.

Thus the synthetic resins may be added to viscose solutions, to cuprammonium spinning solutions or to cellulose acetate solutions.

The finished fibers have exactly thesame properties from the point of view of the colorist as wool. The fastness to light and washing of dyeings thereon with acid wool dyestuils equals that of wool. I

The following examples further serve to illustrate the invention:

Example 1.--500 grams of casein are added in successive small portions while stirring to liters of an aqueous solution of per cent strength of ethyleneimine. This mixture is allowed to stand for 24 hours, during which period the casein enters into reaction with the ethyleneirnine and becomes quickly dissolved. The solution is cooled and 3 kilos of phenylisocyanate are added thereto drop by drop while strongly stirring. The white emulsion first produced gradually solidifies to a fine powder which is insoluble in dilute acids and alkalies. The product contains 22 per cent of nitrogen. It may be added to the spinning solution in the form of an emul- 56 sion produced by making it into a paste with warm cyclohexanol. The thread obtained on spinning is very similar to wool in respect of being dyed.

Example 2.1 kilo of casein is stirred cautiously in small portions into 5 liters of an aqueous solution of 30 per cent strength of ethyleneimine, and the whole is allowed to stand overnight. The mixture is diluted with 2 liters of trichlorethylene and there are added gradually by drops while cooling'and stirring 5 kilos of phenylisocyanate. The white emulsion thus obtained is suspended in 2 liters of cyclohexanol and the whole is heated-for 1 hour at C. 300 grams of this emulsion are added to 10 liters of viscose (cellulose content 7.9 per cent, alkali content 6.3 per cent), and the mixture is stirred until the animalizing agent-has been uniformly distributed in the viscose. The viscose thus obtained, after filtration and subjection to a vacuum, is spun. The animalized fiber has a good afilnity for acid wool dyestufls.

Example 3.-150 grams of casein are mixed with 1 liter of ethyleneimine of 15 per cent strength and after 24 hours the mixture is diluted with 200 cc. of water. 300 cc, of this mixture (proportion of casein to ethyleneimine=1:3) are cooled with ice water and there are added gradually by drops 120 cc. of phenylisocyanate while stirring. The product is an almost transparent highly viscous solution which may be directly emulsified with viscose. The spun fibers have a character similar to that or wool.

Example 4.-300 grams of casein are added in small portionswhile stirring to 1 liter of ethyleneimine of 30 per cent strength. The solution is allowed to stand overnight and then filtered. To the filtrate 300 cc. of phenylisothiocyanate are added drop by drop. When this addition is complete, the whole is heated for 2 hours at 70 C. From the product thus obtained there is prepared an emulsion in cyclohexanol and this is added to viscose.

Example 5.--500 grams of casein are stirred into 3.3 liters of a solution oi ethyleneimine or 15 per cent strength. After a short heating to 40 C. the whole is left standing for 24 hours at room temperature. 'Ihe casein is then completely dissolved. To this mixture of casein and ethyleneimine there are gradually added while stirring 1 liter of phenylisocyanate by drops. The temperature of the reaction mixture must not rise above 40 C. The white reaction product is carefully filtered and well washed with hot water. The condensation product is insoluble in dilute acids and alkalies. It is soluble, for instance, in pyridine, aniline alnd meta-toluidine. ,If this solution is added to a spinning solution fibers of wool-like character are obtained.

What we claim is:

1. Artificial textile materials capable of being dyed by acid wool dyestuffs in the same manner as wool, comprising a polymer useful in forming an artificial textile material incapable per se of being dyed by acid dyes, and finely distributed therein the product of a joint polymerization of the reaction product or an alkyleneimine and a protein, with a compound selected from the group consisting of arylisocyanates and arylisothiocyanates.

assasrs 2. Artificial tame materials capable of being,

dyed by acid wool dyestufls in the same manner as wool, comprising cellulose hydrate, and finely distributed therein the product of a joint polymerization oi the reaction product of an alkyleneimine and a protein, with a compound selected from the group consisting of arylisocyanates and arylisothic :yanates.

3. Artificial textile materials capable of being dyed by acid wool dyestufls in the same manner as wool, comprising cellulose acetate, and finely distributed therein the product of a joint polymerization oi the reaction product of an alkyleneimine and a protein, with a compound selected from the group consisting of arylisocyanates and arylisothiocyanates.

4. Artificial textile materials capable of being dyed by acid wool dyestufls in the same manner as wool, comprising cellulose hydrate, and finely distributed therein the product of a joint polymerization of the reaction product or an alkyleneimine and a protein, with phenylisocyanate.

5. Artificial textile materials capable of being dyed by acid wool dyestufls in the same manner as wool, comprising cellulose hydrate, and finely distributed therein the product of a joint polymerization of the reaction product of ethyleneimine and casein, with phenylisocyanate.

6. Artificial textile materials capable of being dyed by acid wool dyestufls in the same manner as wool, comprising cellulose hydrate, and finely distributed therein the product of a Joint polymerization ot the reaction product of ethyleneimine and casein, with phenylisothiocyanate.

'l. A process of producing artificial textile materials capable of being dyed by acid wool dyestufis, which process comprises finely dispersing in the solution from which the said materials are to be formed, a synthetic resinous composition stable against dilute acids and alkalies, said resinous composition being the product of a joint polymerization of the reaction product of an alkyl eneimine and a protein, with a compound selected from the group consisting of arylisocyanates and arylisothiocyanates.

8. A process of producing artificial textile materials capable of being dyed by acid wool dyestufis, which process comprises finely dispersing in the solution from which the said materials are to be formed, solid particles 01' a synthetic resinous composition stable against dilute acids and alkalies, said resinous composition being the product of a joint polymerization of the reaction product of an alhrleneimine and a protein, with a compound selected from the group consisting of arylisocyanates and arylisothiocyanates.

9. A process of producing artificial textile materials capable of being dyed by acid wool dye- 

